EP0150832A2 - Verfahren zur Herstellung von Verbindungen mit endständiger Doppelbindung - Google Patents
Verfahren zur Herstellung von Verbindungen mit endständiger Doppelbindung Download PDFInfo
- Publication number
- EP0150832A2 EP0150832A2 EP85100784A EP85100784A EP0150832A2 EP 0150832 A2 EP0150832 A2 EP 0150832A2 EP 85100784 A EP85100784 A EP 85100784A EP 85100784 A EP85100784 A EP 85100784A EP 0150832 A2 EP0150832 A2 EP 0150832A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- zirconium oxide
- terminal
- compound
- selectivity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
Definitions
- the present invention relates to a method for producing a compound having a double bond at the terminal (hereinafter referred to as terminal olefin). More particularly, the present invention relates to a method for producing the terminal olefin by dehydration of a compound represented by the formula (I), wherein R is a C 3 - c 20 hydrocarbon group which may have one or more double bonds.
- an olefin can be produced by dehydration of a compound represented by the formula (I).
- the details of the method can be known, for example, from J. Am. Chem. Soc., 85, 2180 (1963), Oil Chemistry, 17, 236 (1968), etc.
- Thorium oxide is known as a catalyst for the selective production of the terminal olefin, but its use in industry is difficult because thorium is a radioactive element so that there occurs a serious problem of safety in handling thorium oxide as a catalyst.
- the present inventors extensively studied to overcome the defects of the conventionally well-known catalyst, i.e.,
- An object of the present invention is to provide a method for producing terminal olefinsat low costs and with safety which is useful as a material for heat-resistant polymers, a comonomer for polyolefins, a raw material for detergents and the like.
- the accompanying drawing shows the relationship between the total content of silicon dioxide and titanium dioxide and the selectivity of vinylcyclohexane.
- the starting material used in the method of the present invention is a compound represented by the formula (I), wherein R is a C 3 - C 20 hydrocarbon group which may have one or more double bonds.
- R is not particularly limited so far as it is a C 3 - C 20 hydrocarbon group, but it is preferably a C 3 - C 10 hydrocarbon group and more preferably a C 3 -C 10 saturated hydrocarbon group.
- 4-methyl-2-pentanol and 1-cyclohexylethanol are most preferred.
- the OH group and the hydrogen atom of the methyl group in the formula (I) are released in the form of water to selectively produce the terminal olefin.
- zirconium compounds are produced by various methods using Zircon, Baddeleyite, etc. as a raw material, but complete removal of silicon, titanium, aluminum, iron, etc. contained in raw ores is so difficult that it is usual for zircornium products to contain these impurities in trace amounts.
- the zirconium oxide used in the present invention is of high purity, and that it does not contain particularly silicon and titanium among these impurities so far as possible.
- the total content, as oxide, of the both metals is 0.3 wt.% or less, a sufficient selectivity is obtained in the production of the terminal olefin, and when the total content is 0.1 wt.% or less, a more preferred selectivity is obtained.
- Zirconium oxide used in the present invention is obtained by various methods, and particularly, one obtained by calcination of zirconium compounds at 300° to 1500°C is preferred.
- preferred examples of zirconium compound used for calcination include for example zirconium hydroxide, zirconyl hydroxide, zirconium nitrate, zirconyl nitrate, zirconyl carbonate, zirconium alkoxide and the like. These compounds may be calcined in a state wherein they are supported on suitable carriers, or zirconium oxide after calcination may be supported on suitable carriers.
- zirconium oxide itself after calcination as a catalyst without using carriers. It is also possible to prepare the catalyst in the coexistence of a second component such as yttrium, etc. if necessary.
- the calcination temperature is generally 300° to 1500°C, but preferably, a temperature of 500° to 1100°C is employed.
- the calcination time is generally 0.1 to 50 hours, but preferably, a period of time of 1 to 10 hours is employed. Generally, the activity tends to lower as the calcination temperature becomes high, and sufficient activity comes to fail to appear when the temperature exceeds 1500°C.
- a method of reaction is not particularly limited, but generally, a gas-phase reaction of fixed-bed form or fluidized-bed form is employed.
- the reaction temperature is generally 200° to 500°C, but preferably, a temperature of 300° to 400°C is employed.
- the reaction pressure is not particularly limited, and the reaction may be carried out at atmospheric pressure or under pressure a little higher than that. If necessary, a method may also be employed in which the starting material (I) is reacted in dilution with an inert gas such as nitrogen, etc. The reaction under a reduced pressure also gives a good result.
- a rate of 0.1 to 15 hr -1 preferably 0.5 to 5 hr as expressed by LHSV, is employed.
- a hard glass tubular reactor of 12.5 mm in internal diameter having at the center a tubular sheath of.4 mm in external diameter for temperature measurement was packed with 12 ml of a zirconia catalyst, which had been prepared by calcination of zirconium hydroxide having a particle size of 0,7 to 1,7nm at 1000°C for 2 hours, and externally heated in an electric furnace.
- a zirconia catalyst which had been prepared by calcination of zirconium hydroxide having a particle size of 0,7 to 1,7nm at 1000°C for 2 hours, and externally heated in an electric furnace.
- the reaction gas from the tubular reactor was analyzed by gas chromatography.
- Example 1 Experiments with various kinds of alcohol were carried out in the same manner as in Example 1 except that the amount of catalyst used was 4 ml; the alcohol, a starting material, was supplied together with 0.4 1/min of nitrogen gas; and the zirconium oxide catalyst used was prepared by calcining zirconyl nitrate [ZrO(NO 3 )2 2H 2 0] at 1000°C for 2 hours, and its Sio 2 and TiO 2 contents were 0.05 wt.% or less and 0.01 wt.% or less, respectively. The results are shown in Table 1.
- a hard glass tubular reactor of 19 mm in internal diameter having at the center a tubular sheath of 6 mm in external diameter for temperature measurement was packed with 27 ml of a zirconia catalyst, which had been prepared by calcination of zirconium hydroxide having a particle size of 0,7 to 1,7 mm at 1000°C for 2 hours, and externally heated in an electric furnace.
- a zirconia catalyst which had been prepared by calcination of zirconium hydroxide having a particle size of 0,7 to 1,7 mm at 1000°C for 2 hours, and externally heated in an electric furnace.
- the reaction gas from the tubular reactor was trapped and analyzed by gas chromatography.
- a stainless steel tubular reactor of 16 mm in internal diameter having at the center a tubular sheath of 4 mm in external diameter for temperature measurement was packed with 30 ml of zirconium oxide having a particle size of 0,7 to 1,7 mm and externally heated in an electric furnace.
- the reaction gas from the reactor was trapped and analyzed by gas chromatography.
- a stainless steel tubular reactor of 4 mm in internal diameter was packed with 7.4 ml of a zirconia catalyst prepared by calcination of zirconium hydroxide having a particle size of 0,7 to 1,7 mm at 500°C for 2 hours, and externally heated in an electric furnace.
- a zirconia catalyst prepared by calcination of zirconium hydroxide having a particle size of 0,7 to 1,7 mm at 500°C for 2 hours, and externally heated in an electric furnace.
- the reaction gas from the reactor was analyzed by gas chromatography.
- a stainless steel tubular reactor of 8 mm in internal diameter was packed with 50 ml of a zirconia catalyst which had been prepared by calcination of zirconium hydroxide having a particle size of 0,7 to 1,7 mm at 400°C for 2 hours, and externally heated in an electric furnace.
- a zirconia catalyst which had been prepared by calcination of zirconium hydroxide having a particle size of 0,7 to 1,7 mm at 400°C for 2 hours, and externally heated in an electric furnace.
- the reaction gas from the reactor was analyzed by gas chromatography.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59013920A JPS60158121A (ja) | 1984-01-27 | 1984-01-27 | ビニルシクロヘキサンの製造方法 |
JP13920/84 | 1984-01-27 | ||
JP59177217A JPS6153230A (ja) | 1984-08-24 | 1984-08-24 | 末端に二重結合を有する化合物の製造方法 |
JP177217/84 | 1984-08-24 | ||
JP252298/84 | 1984-11-28 | ||
JP59252298A JPS61130240A (ja) | 1984-11-28 | 1984-11-28 | 末端に二重結合を有する化合物の製法 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0150832A2 true EP0150832A2 (de) | 1985-08-07 |
EP0150832A3 EP0150832A3 (en) | 1986-03-19 |
EP0150832B1 EP0150832B1 (de) | 1988-11-02 |
Family
ID=27280453
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19850100784 Expired EP0150832B1 (de) | 1984-01-27 | 1985-01-25 | Verfahren zur Herstellung von Verbindungen mit endständiger Doppelbindung |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0150832B1 (de) |
CA (1) | CA1235144A (de) |
DE (1) | DE3565977D1 (de) |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0222356A1 (de) * | 1985-11-11 | 1987-05-20 | Sumitomo Chemical Company, Limited | Verfahren zur Herstellung von Verbindungen mit endständiger Doppelbindung |
US5057637A (en) * | 1990-06-22 | 1991-10-15 | Chevron Research And Technology Company | Process for producing C5 to C18 straight chain α-olefins from the corresponding internal olefins |
US5057638A (en) * | 1990-06-22 | 1991-10-15 | Chevron Research And Technology Company | Process for making 1-hexene from 1-butene |
US5057636A (en) * | 1990-06-22 | 1991-10-15 | Chevron Research And Technology Company | Process for recovering N-hexenes from a mixture of C6 olefin isomers by oligomerizing the branched-chain C6 olefin isomers in the mixture using a moderate strength acid catlyst |
US5059733A (en) * | 1990-06-22 | 1991-10-22 | Chevron Research And Technology Company | Process for making 1-hexene and high octane blending components |
US5059734A (en) * | 1990-06-22 | 1991-10-22 | Chevron Research And Technology Company | Process for selectively producing C5 to C18 straight chain α olefins |
US5130287A (en) * | 1990-06-22 | 1992-07-14 | Chevron Research And Technology Company | Method of making a hydrous zirconium oxide dehydration catalyst and product prepared by the method |
WO2001044145A1 (en) * | 1999-12-14 | 2001-06-21 | Fortum Oil And Gas Oy | Method for the manufacture of olefins |
KR100688797B1 (ko) | 2003-12-15 | 2007-02-28 | 에스케이 주식회사 | 2차 알코올의 탈수반응에 의한 알파-올레핀의 제조방법 |
WO2012016787A1 (en) | 2010-08-03 | 2012-02-09 | Total Petrochemicals Research Feluy | Process to make olefins from isobutanol |
WO2012016786A1 (en) | 2010-08-03 | 2012-02-09 | Total Petrochemicals Research Feluy | Process to make olefins from isobutanol |
WO2012016785A1 (en) | 2010-08-03 | 2012-02-09 | Total Petrochemicals Research Feluy | Combined process to make olefins from isobutanol |
CN103333038A (zh) * | 2013-07-19 | 2013-10-02 | 沈阳市宏城精细化工厂 | 一种生产长碳链α线性烯烃的方法 |
US9469575B2 (en) | 2011-12-15 | 2016-10-18 | Dow Global Technologies Llc | Non-reductive dehydroxylation of vicinal compounds to olefins using a halogen-based catalyst |
US9968914B2 (en) | 2012-12-26 | 2018-05-15 | Kao Corporation | Method for producing olefin |
WO2023214001A1 (fr) | 2022-05-06 | 2023-11-09 | Totalenergies Onetech | Procédé d'obtention d'hydrocarbures, et installation associée |
WO2023214015A1 (fr) | 2022-05-06 | 2023-11-09 | Totalenergies Onetech | Procédé de fabrication d'un carburéacteur, carburéacteur et installation associés |
WO2023214014A1 (fr) | 2022-05-06 | 2023-11-09 | Totalenergies Onetech | Procédé de fabrication d'un carburéacteur comprenant une étape de conversion d'un flux d'alcool dans un lit fluidisé, carburéacteur et installation associés |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011084550A (ja) * | 2009-09-17 | 2011-04-28 | Sumitomo Chemical Co Ltd | 二重結合を有する化合物の製造方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH421077A (fr) * | 1962-12-20 | 1966-09-30 | Continental Oil Co | Procédé de production d'alpha-oléfines par déshydratation d'alcools secondaires |
US4490567A (en) * | 1982-04-08 | 1984-12-25 | Phillips Petroleum Company | Catalyst and process for dehydrating 2-alcohols |
-
1985
- 1985-01-25 DE DE8585100784T patent/DE3565977D1/de not_active Expired
- 1985-01-25 EP EP19850100784 patent/EP0150832B1/de not_active Expired
- 1985-01-25 CA CA000472876A patent/CA1235144A/en not_active Expired
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH421077A (fr) * | 1962-12-20 | 1966-09-30 | Continental Oil Co | Procédé de production d'alpha-oléfines par déshydratation d'alcools secondaires |
US4490567A (en) * | 1982-04-08 | 1984-12-25 | Phillips Petroleum Company | Catalyst and process for dehydrating 2-alcohols |
Non-Patent Citations (1)
Title |
---|
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 85, 1963, Easton A.J. LUNDEEN et al. "Selective catalytic dehydration of 2-alcohols; a new synthesis of 1-olefins" pages 2180-2181 * |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0222356A1 (de) * | 1985-11-11 | 1987-05-20 | Sumitomo Chemical Company, Limited | Verfahren zur Herstellung von Verbindungen mit endständiger Doppelbindung |
US5059733A (en) * | 1990-06-22 | 1991-10-22 | Chevron Research And Technology Company | Process for making 1-hexene and high octane blending components |
US5057636A (en) * | 1990-06-22 | 1991-10-15 | Chevron Research And Technology Company | Process for recovering N-hexenes from a mixture of C6 olefin isomers by oligomerizing the branched-chain C6 olefin isomers in the mixture using a moderate strength acid catlyst |
US5057637A (en) * | 1990-06-22 | 1991-10-15 | Chevron Research And Technology Company | Process for producing C5 to C18 straight chain α-olefins from the corresponding internal olefins |
US5059734A (en) * | 1990-06-22 | 1991-10-22 | Chevron Research And Technology Company | Process for selectively producing C5 to C18 straight chain α olefins |
US5130287A (en) * | 1990-06-22 | 1992-07-14 | Chevron Research And Technology Company | Method of making a hydrous zirconium oxide dehydration catalyst and product prepared by the method |
US5057638A (en) * | 1990-06-22 | 1991-10-15 | Chevron Research And Technology Company | Process for making 1-hexene from 1-butene |
WO2001044145A1 (en) * | 1999-12-14 | 2001-06-21 | Fortum Oil And Gas Oy | Method for the manufacture of olefins |
KR100688797B1 (ko) | 2003-12-15 | 2007-02-28 | 에스케이 주식회사 | 2차 알코올의 탈수반응에 의한 알파-올레핀의 제조방법 |
WO2012016787A1 (en) | 2010-08-03 | 2012-02-09 | Total Petrochemicals Research Feluy | Process to make olefins from isobutanol |
WO2012016786A1 (en) | 2010-08-03 | 2012-02-09 | Total Petrochemicals Research Feluy | Process to make olefins from isobutanol |
WO2012016785A1 (en) | 2010-08-03 | 2012-02-09 | Total Petrochemicals Research Feluy | Combined process to make olefins from isobutanol |
US9056806B2 (en) | 2010-08-03 | 2015-06-16 | Total Research & Technology Feluy | Process to make olefins from isobutanol |
US9056807B2 (en) | 2010-08-03 | 2015-06-16 | Total Research & Technology Feluy | Process to make olefins from isobutanol |
US9079813B2 (en) | 2010-08-03 | 2015-07-14 | Total Research & Technology Feluy | Process to make propylene from isobutanol by dehydration and subsequent cracking |
US9469575B2 (en) | 2011-12-15 | 2016-10-18 | Dow Global Technologies Llc | Non-reductive dehydroxylation of vicinal compounds to olefins using a halogen-based catalyst |
US9968914B2 (en) | 2012-12-26 | 2018-05-15 | Kao Corporation | Method for producing olefin |
CN103333038B (zh) * | 2013-07-19 | 2015-07-15 | 沈阳市宏城精细化工厂 | 一种生产长碳链α线性烯烃的方法 |
CN103333038A (zh) * | 2013-07-19 | 2013-10-02 | 沈阳市宏城精细化工厂 | 一种生产长碳链α线性烯烃的方法 |
WO2023214001A1 (fr) | 2022-05-06 | 2023-11-09 | Totalenergies Onetech | Procédé d'obtention d'hydrocarbures, et installation associée |
WO2023214015A1 (fr) | 2022-05-06 | 2023-11-09 | Totalenergies Onetech | Procédé de fabrication d'un carburéacteur, carburéacteur et installation associés |
WO2023214014A1 (fr) | 2022-05-06 | 2023-11-09 | Totalenergies Onetech | Procédé de fabrication d'un carburéacteur comprenant une étape de conversion d'un flux d'alcool dans un lit fluidisé, carburéacteur et installation associés |
FR3135265A1 (fr) | 2022-05-06 | 2023-11-10 | Totalenergies Onetech | Procédé d’obtention d’hydrocarbures, et installation associée |
FR3135264A1 (fr) | 2022-05-06 | 2023-11-10 | Totalenergies Onetech | Procédé de fabrication d’un carburéacteur, carburéacteur et installation associés |
FR3135263A1 (fr) | 2022-05-06 | 2023-11-10 | Totalenergies Onetech | Procédé de fabrication d’un carburéacteur comprenant une étape de conversion d’un flux d’alcool dans un lit fluidisé, carburéacteur et installation associés |
Also Published As
Publication number | Publication date |
---|---|
CA1235144A (en) | 1988-04-12 |
EP0150832A3 (en) | 1986-03-19 |
DE3565977D1 (en) | 1988-12-08 |
EP0150832B1 (de) | 1988-11-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0150832B1 (de) | Verfahren zur Herstellung von Verbindungen mit endständiger Doppelbindung | |
CA1211098A (en) | Conversion of methane to olefins and hydrogen | |
EP0498573B1 (de) | Verfahren zur Herstellung von Propylene | |
US4367342A (en) | Olefin epoxidation | |
US5407888A (en) | Silver catalyst | |
EP0082641B1 (de) | Katalysatoren für die Herstellung von Alkoholen aus Olefinen und Synthesegas und solche Katalysatoren verwendendes Verfahren | |
EP0434485B1 (de) | Verfahren zur Herstellung von Phenol | |
EP1473083B1 (de) | Verfahren zur Herstellung von aktivierten Methathesekatalysatoren | |
WO2001090043A1 (en) | Process for the production of vinyl acetate | |
WO2014199349A2 (en) | Metal impregnated amorphous silicates for the selective conversion of ethanol to butadiene | |
EP0441430A1 (de) | Katalytische Dehydrierung von C2-C5-Paraffinen | |
US5518699A (en) | Method of carrying out chemical reactions in reaction distillation columns | |
EP0506428B1 (de) | Synthese von Methyl-t-butylether unter Verwendung von mit Sulfaten oder Schwefelsäure behandelten Oxiden der Gruppe IV | |
EP0037149A1 (de) | Verfahren zur Herstellung von Aldehyden | |
US4338471A (en) | Process for preparing phenol | |
US20100197978A1 (en) | IPA From Propylene Using Mixed Metal Oxides | |
KR100567616B1 (ko) | 고리형 지방족 옥심의 제조방법 | |
US4894467A (en) | Vapor phase oxidation or styrene to styrene oxide | |
US4754092A (en) | Reducing methane production and increasing liquid yields in Fischer-Tropsch reactions | |
JPS63248448A (ja) | 触媒の製造方法およびオリゴマー化方法 | |
CA1068727A (en) | Ethynylation catalyst and process for producing alkynols | |
US5210336A (en) | Oxidation of olefin to glycol | |
US5106810A (en) | Methanol dissociation catalysts | |
JP2585737B2 (ja) | テルペンアルコ―ルの製造方法 | |
US4238371A (en) | Methanation catalyst |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): DE FR GB IT NL |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): DE FR GB IT NL |
|
17P | Request for examination filed |
Effective date: 19860820 |
|
17Q | First examination report despatched |
Effective date: 19870603 |
|
ITF | It: translation for a ep patent filed |
Owner name: FIAMMENGHI - DOMENIGHETTI |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB IT NL |
|
REF | Corresponds to: |
Ref document number: 3565977 Country of ref document: DE Date of ref document: 19881208 |
|
ET | Fr: translation filed | ||
RAP4 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: SUMITOMO CHEMICAL COMPANY, LIMITED |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
ITTA | It: last paid annual fee | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20031208 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20031211 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20031212 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20031215 Year of fee payment: 20 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20050124 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20050125 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 |
|
NLV7 | Nl: ceased due to reaching the maximum lifetime of a patent |
Effective date: 20050125 |